ES2324154T3 - COMPOUNDS OF N- (1,2,4 TRIAZOLOAZINIL) THIOPHENOSULPHONAMIDE AS HERBICIDES. - Google Patents

Abstract

A compound of N- (triazoloazinyl) thiophenesulfonamide of the formula (I): ** see formula ** in which X represents CH or N; Y represents CZ or N, with the proviso that X and Y are not both N; W represents H or OR, with the proviso that when Y is CZ, then W is H; Z represents R, OR or halo; D and E represent S or CB, with the proviso that one of D or E is S; A represents OR '' or CO2R '' '', and B represents H, halo, CF3, R or R 7 or CO2R '' ''; T represents H, SO 2R '' '', C (O) R '' '', C (O) OR '' '', C (O) NR '' '' 2 or CH 2CH 2C (O) OR ' '' '; R represents CH3 or CH2CH3; R '' represents C 1 -C 4 alkyl, C 3-C 4 alkenyl or C 3-C 4 alkynyl, each optionally having up to two chloro, bromine or O-alkyl (C1-C4) substituents or up to the maximum possible number of fluoro substituents; R '' '' represents H or C1-C4 alkyl; and, when T represents H, its agriculturally acceptable salts.

Description

Compounds of N- (1,2,4 triazoloazinyl) thiophenesulfonamide as herbicides.

The present invention relates to compounds of substituted thiophenesulfonamide, to herbicidal compositions that contain the compounds and the usefulness of the compounds for the unwanted vegetation control.

Control of unwanted vegetation through chemical agents, that is, herbicides, is an important aspect of Agriculture and exploitation of modern lands. Although they know many chemicals that are useful for controlling unwanted vegetation, new compounds that are more desirable generally effective, be more effective for specific species of plants, be less harmful to desirable vegetation, be more safe for man or the environment, be less expensive than use or have other advantageous attributes.

Many compounds of substituted benzenesulfonamide and it is known that some of them possess herbicidal activity For example, certain compounds of N - ([1,2,4] triazolo [1,5-a] pyrimidin-2-yl) benzenesulfonamide and its herbicidal utility were described in US Pat. UU. 4,638,075 and certain compounds of N - ([1,2,4] triazolo [1,3,5] triazin-2-yl) benzenesulfonamide  They were described in US Pat. UU. 4,685,958. In addition, certain composed of N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl) benzenesulfonamide, N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl) pyridinsulfonamide, N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl) benzenesulfonamide  Y N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl) pyridinsulfonamide They were described in US Pat. UU. 5,858,924. Some N-phenylarylsulfonamide compounds are also They know and are known to possess herbicidal activity. For example, certain compounds of N- (phenyl substituted) [1,2,4] triazolo [1,5-c] pyrimidin-2-sulfonamide They were described in US Pat. UU. 5,163,995 and certain N- (phenyl compounds substituted) [1,2,4] triazolo [1,5-a] pyridin-2-sulfonamide  They were described in US Pat. UU. 5,571,775.

It has now been found that a new class N- (triazoloazinyl) thiophenesulfonamide compounds which comprises compounds of N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl) thiophenesulfonamide, N - ([1,2,4] triazolo [1,5-a] pyrimidin-2-yl) thiophenesulfonamide  Y N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl) thiophenesulfonamide they are potent herbicides for the control of unwanted vegetation by applying either pre-emergency or post-emergency. The invention includes compounds of N- (triazoloazinyl) thiophenesulfonamide of Formula I:

one

       \ vskip1.000000 \ baselineskip
    

in the that

X represents CH or N;

Y represents CZ or N, with the proviso that X e And they are not both N;

W represents H or OR, with the proviso that when Y is CZ, then W is H;

Z represents R, OR or halo;

D and E represent S or CB, with the condition of that one of D or E is S;

A represents OR 'or CO 2 R' 'and B represents independently H, halo, CF 3, R, OR 'or CO 2 R' ';

T represents H, SO2R '', C (O) R '', C (O) OR '', C (O) NR '' 2 or CH 2 CH 2 C (O) OR '';

R represents CH 3 or CH 2 CH 3;

R 'represents alkyl C 1 -C 4, alkenyl C 3 -C 4 or alkynyl C_ {3} -C_ {4}, each optionally possessing Up to two substituents chlorine, bromine or O (C 1 -C 4) alkyl or up to the maximum possible number of fluoro substituents;

R '' represents H or alkyl C 1 -C 4;

and, when T represents H, its salts agriculturally acceptable.

Compounds in which A represents OR 'or B represents CO 2 R '' when D represents S and T represents H are among the preferred compounds of the invention.

The invention further includes compositions that contain herbicidal amounts of compounds of Formula I in combination with one or more agricultural adjuvants or vehicles acceptable and the use of the compounds of Formula I as herbicides. The use of suitable compounds of the invention to achieve total vegetation control. They can control both herbaceous and broadleaf weeds. Be generally prefers the application of preemergence of compounds to undesirable vegetation.

The compounds of N- (triazoloazinyl) thiophenesulfonamide of the invention can generally described as compounds of N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl) thiophenesulfonamide, N - ([1,2,4] triazolo [1,5-a] pyrimidin-2-yl) thiophenesulfonamide  Y N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl) thiophenesulfonamide replaced. They can be characterized as compounds of substituted thiophenesulfonamide that they possess, on the atom of amide nitrogen, a remainder of [1,2,4] triazolo [1,5-c] pyrimidin-2-yl  replaced, [1,2,4] triazolo [1,5-a] pyrimidin-2-yl replaced or [1,2,4] triazolo [1,5-a] pyridin-2-yl replaced.

The herbicidal compounds of the invention are N- (triazoloazinyl) thiophenesulfonamide compounds of Formula  generic I:

       \ vskip1.000000 \ baselineskip
    

2

       \ vskip1.000000 \ baselineskip
    

Such compounds in which X represents N they contain a rest of N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl)  substituted, those in which Y represents N contain a remainder from N - ([1,2,4] triazolo [1,5-a] pyrimidin-2-yl)  substituted and those in which X represents C-H and And represents C-Z contain a remainder of N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl)  replaced. The compounds in which E represents S are compounds of 2-thiophenesulfonamide and the compounds in which D represents S are compounds of 3-thiophenesulfonamide. The compounds are characterized also for having a methoxy or ethoxy substituent adjacent to the bridgehead nitrogen in the 6-membered ring portion of the triazoloazine ring and for having at least one substituent (A) adjacent to the sulfonamide in the thiophene ring.

The compounds of the invention include compounds of Formula I in which X is N or CH. Often preferred  compounds in which X is N. However, sometimes preferred the compounds in which X is CH.

The compounds of the invention include compounds of Formula I in which Y is N, provided that X is not also N or CZ, in which Z is methyl, ethyl, methoxy, ethoxy or halo. Compounds in which Y is CZ are often preferred. Without However, compounds in which Y is N. are sometimes preferred. Compounds in which Z is methoxy are often preferred.

The compounds of the invention include compounds of Formula I in which D and E represent S or CB, with such of one and only one of D or E is S. Usually preferred are thiophene-3-sulfonamides in which D represents S.

The compounds of the invention include compounds of Formula I in which B represents H, halo, CF 3, R, OR 'or CO 2 R' ', and A is OR' or CO 2 R '', and most preferably OR '.

The compounds of the invention include compounds of Formula I in which W represents H or OR, provided that when Y is CZ, W is H. When Y is N, W is preferably methoxy

For the compounds of the present invention, R it can be CH 3 or CH 2 CH 3. For OR, R is preferably  CH_ {3}.

For the compounds of the present invention, R ' it can be C 1 -C 4 alkyl, alkenyl C 3 -C 4 or alkynyl C_ {3} -C_ {4}, each optionally possessing Up to two substituents chlorine, bromine or O (C 1 -C 4) alkyl or up to the maximum possible number of fluoro substituents. For OR ', R' it is preferably C 1 -C 4 alkyl which optionally has up to two substituents chlorine, bromine or O (C 1 -C 4) alkyl or up to the maximum possible number of fluoro substituents.

Compounds of Formula I include those in those that T represents hydrogen, an alkylsulfonyl group (SO2R ''), an acyl group (C (O) R ''), a group alkoxycarbonyl (C (O) OR ''), an aminocarbonyl group (C (O) NR '' 2) or a group 2- (alkoxycarbonyl) ethyl (CH 2 CH 2 C (O) OR ''). such are preferred compounds in which T represents hydrogen. The invention includes in addition the agriculturally acceptable salts of compounds of the Formula I in which T represents hydrogen.

For the compounds of the present invention, R '' may be H or C 1 -C 4 alkyl. R '' is preferably CH 3 or CH 2 CH 3.

It is also considered that the compounds of Formula I possessing every possible combination of substituents preferred, most preferred, most preferred, desirable and of Of special interest are important embodiments of the invention.

The terms alkyl, alkenyl and alkynyl (including when modified as in haloalkyl and alkoxy), as used herein, include chain groups linear, branched chain and cyclic. Thus, typical alkyl groups they are methyl, ethyl, 1-methyl ethyl, propyl, 1,1-dimethylethyl and cyclopropyl. I often know They prefer methyl and ethyl. The alkyl groups are sometimes referred to as the present memory normal (n), iso (i), secondary (s) or tertiary (t). A typical alkyl with up to the maximum possible number of fluoro substituents includes trifluoromethyl, monofluoromethyl, 2,2,2-trifluoroethyl, 2,3-difluoropropyl and the like; I often know prefers trifluoromethyl. The term halogen includes fluorine, Chlorine, bromine and iodine.

The term agriculturally acceptable salts is used herein to indicate compounds in which the Sulfonamide acid proton of the compound of Formula I is it replaces with a cation that by itself is not herbicidal for crop plants that are treated neither significantly harmful for the applicator, the environment or the end user of Any crop in question. Suitable cations include, by for example, alkali metal or alkaline earth metal derivatives and Ammonia derivatives and amines. Preferred cations include sodium, potassium, magnesium and aminium cations of formula:

R 2 R 3 R 4 NH +

in which R 2, R 3 and R 4 each independently represent hydrogen or alkyl (C 1 -C 12), cycloalkyl (C 3 -C 12) or alkenyl (C_ {3} -C_ {12}), each of which is optionally substituted with one or more hydroxy, alkoxy groups (C 1 {C 8}), (C 1 -C 8) alkyl - uncle or phenyl; provided that R 2, R 3 and R 4 are sterically compatible. Additionally, any two of R 2, R 3 and R 4 together can represent a residue aliphatic difunctional containing 1 to 12 carbon atoms and up to two atoms of oxygen or sulfur. Salts of the compounds of Formula I they can be prepared by treating compounds of Formula I in which V represents hydrogen with a metal hydroxide, such as sodium hydroxide, potassium hydroxide or magnesium hydroxide, or an amine, such as ammonia, trimethylamine, hydroxyethylamine, bisalylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine

The compounds of Table 1 and 2 are examples of the compounds of the invention. Some of the compounds specifically preferred of Formula I, which vary depending on the weed species to be controlled, the crop present (if any) and other factors, include the following Compounds of Table 1 and 2: N- (5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-yl) -4-methoxythiophene-3-sulfonamide  Y N- (5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-yl) -2-carboxymethylthiophene-3-sulfonamide.

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

       \ newpage
    

3

       \ newpage
    

4

5

       \ newpage
    

6

       \ newpage
    

The compounds of Formula I in which T represents hydrogen can be prepared by reacting a compound 2-amino [1,2,4] substituted triazoloazine of Formula II:

       \ vskip1.000000 \ baselineskip
    

7

       \ vskip1.000000 \ baselineskip
    

with a chloride compound of thiophenesulfonyl of Formula III:

       \ vskip1.000000 \ baselineskip
    

8

       \ vskip1.000000 \ baselineskip
    

in which A, D, E, R, W, X and Y are as defined for compounds of Formula I. The reaction may carried out by combining molar amounts approximately equal of the two compounds in a polar aprotic solvent, such as acetonitrile, and add pyridine and a catalytic amount (5 to 25 mole percent sulfonyl chloride compound) of dimethylsulfoxide at room temperature. They are added, if necessary,  sulfonyl chloride, pyridine and dimethylsulfoxide compound additional to complete the reaction. The reactions lead from A few hours to several days to reach completion. Be employ means to exclude moisture, such as an atmosphere of dry nitrogen The compounds of Formula I obtained, which are solids with low solubility in many organic solvents common and in water, can be recovered using media conventional.

The compounds of N- (triazoloazinyl) thiophenesulfonamide of Formula I in which T represents something other than hydrogen can be prepared from the corresponding compounds of Formula I in which T represents hydrogen by acylation under known reaction conditions in the art for sulfonamide acylation reactions related. Suitable acylating agents include compounds of alkanoyl chloride, such as propionyl chloride or trifluoroacetyl; chloroformate ester compounds, such as 2-methoxyethyl chloroformate; composed of carbamoyl chloride, such as N ', N'-diallylcarbamoyl, and isocyanate compounds alkyl, such as isocyanate 2-chloroethyl.

The compounds of Formula I that have alkoxy substituents on the triazoloazine ring can be prepared  from the corresponding halogenated compounds of Formula I by treatment with a suitable alkoxide using the General methods known in the art for such substitutions. Halo substituents in some positions are replaced more easily than halo substituents in other positions, depending on the triazoloazine ring system, and may selectively replace

Many compounds of 2-amino [1,2,4] triazolo [1,5-a] pyridine of Formula II (X represents C-H and Y represents C-Z) can be prepared by the reaction of composed of N- (2-pyridinyl) -N'-carboethoxythiourea Properly substituted formula:

       \ vskip1.000000 \ baselineskip
    

9

       \ vskip1.000000 \ baselineskip
    

in which Z is as defined for Compounds of Formula I and L is OR or halo, with hydroxylamine. The reaction is typically carried out in a solvent such as ethanol and requires heating for a few hours. The hydroxylamine is typically generated by neutralizing the hydrochloride with a hindered tertiary amine, such as diisopropylethylamine, or an alkali metal alkoxide, such as sodium ethoxide The desired Formula II compounds may recover by conventional means, such as by removal of volatile components from the reaction mixture by evaporation, and can be purified by means conventional, such as by extraction with water and / or others solvents in which they are poorly soluble. Starting materials of the compound of N- (2-pyridinyl) -N'-carboethoxythiourea for this method can be obtained by treating 2-aminopyridine compounds appropriately substituted with ethoxycarbonyl isothiocyanate. The reaction is generally carried out in an inert organic solvent to ambient temperatures The global method is further described. in US Pat. UU. 5,571,775.

The starting materials of compounds of 2-substituted aminopyridine for the described method previously known in the art or can be prepared by the methods described herein or by methods generals known in the art.

Compounds of Formula II in which X represents CH can also be prepared from appropriately substituted 2-cyanoaminopyridine compounds by the method described by B. Vercek et al . in Monatshefte fur Chemie , 114 , 789-798 (1983). Additional preparation methods of such compounds were described by KT Potts et al . in Journal of Organic Chemistry , 31 , 265-273 (1966).

The compounds of Formula II in which X represents N, that is, compounds of 2-amino [1,2,4] triazolo [1,5-c] pyrimidine,  they can be prepared from compounds of 4-Hydrazinopyrimidine of the formula:

       \ vskip1.000000 \ baselineskip
    

10

       \ vskip1.000000 \ baselineskip
    

in which Q represents methylthio or Chlorine and Z is as defined for compounds of Formula I. The Hydrazinopyrimidine compound is first treated with cyanogen bromide to produce the hydrobromide of a compound from 3-amino- [1,2,4] triazolo [4,3-c] pyrimidine (substituted in 8-substituted in 5) of the formula:

       \ vskip1.000000 \ baselineskip
    

eleven

in which Q represents methylthio or Chlorine and Z is as defined for compounds of Formula I. The reaction is generally carried out in an organic solvent, such as isopropyl alcohol, at room temperature. The products can be recovered by conventional means, such as at add a non-polar solvent, for example diethyl ether, and collect the solid that forms by filtration. The products previous intermediates in which Q represents methylthio can then become the desired compounds of Formula II in which Q represents an alkoxy group by treatment with an alkali metal alcoholate, such as sodium methylate or ethylate potassium, and ethyl acrylate in the corresponding alcohol as a solvent The compound is transposed and the methylthio moiety is replaces with the alkoxy moiety derived from the alcohol in the medium. The reaction is usually carried out at temperatures below 25 ° C The desired compounds of Formula II can be recovered by neutralization with acetic acid and collecting the solid that It is formed by filtration or other conventional means. The compounds of Formula II in which X represents N and Q represents Chlorine can be obtained from the intermediate product [4,3-c] corresponding in which Q represents chlorine  by isomerization with a trialkylamine base. The starting materials of compounds of 4-Hydrazinopyrimidine for these methods can be prepared from the compounds of Corresponding 4-chloropyrimidine, which are good known in the art, by reaction with hydrazine

Other methods of preparing compounds of Formula II in which X represents N are described by GW Miller et al ., J. Chemical Society , 1965, page 3357, and 1963, page 5642.

The compounds of Formula II in which Y represents N, for example, compounds of 2-amino [1,2,4] triazolo [1,5-a] pyrimidine,  can be prepared by the reaction of N- (4,6-dialkoxypyrimidin-2-yl) -N'-carboethoxythiourea of the formula:

12

in which R is as defined for Formula I with hydroxylamine. The reaction is carried out. typically in a solvent such as ethanol and requires heating for a few hours. Hydroxylamine is generated typically by neutralizing the hydrochloride with a hindered tertiary amine, such as diisopropylethylamine, or a alkali metal alkoxide, such as sodium ethoxide. The compound of desired Formula II can be recovered by conventional means, such as by removing volatile components from the reaction mixture by evaporation, and can be purified by conventional means, such as by extraction with water and / or other solvents in which it is poorly soluble. The material of departure of N- (4,6-dialkoxypyrimidin-2-yl) -N'-carboethoxythiourea for this method can be obtained by treating 2-amino-4,6-dialkoxypyrimidine with ethoxycarbonyl isothiocyanate. The reaction is carried out. generally in an inert organic solvent at temperatures ambient. The overall method is further described in the Patent. from the USA UU. 5,571,775.

The starting material of 2-amino-4,6-dialkoxypyrimidine For the method described above it is known in the art.

Chloride starting materials of Substituted thiophenesulfonyl of Formula III can be prepared by the methods described herein or by general or specific methods known in the art. Many of such compounds can be prepared by lithiation of the corresponding thiophene compound with butyl aluminum, the reaction of the compound of thienyl lithium obtained with SO2 and chlorination with N-chlorosuccinimide. In each of these stages of reaction, conditions generally known for such were used procedures The thienyl chloride compounds can also prepare by exchange reactions halogen metal halothiophenes with n-butyllithium Many propil- o benzyl thiophene can also be prepared by alkylation of the mercaptothiophene compound corresponding using standard methods or by reacting thienyl lithium compounds with disulfide appropriate. Subsequent chloroxidation with, for example, chlorine in presence of water provides sulfonyl chlorides desired

Compounds of Formula III include chloride compounds thiophene-2-sulfonyl substituted by the formula:

13

       \ vskip1.000000 \ baselineskip
    

and chloride compounds of thiophene-3-sulfonyl substituted by the formula:

14

in which A and B are defined as previously.

Although it is possible to use the compounds of N- (triazoloazinyl) thiophenesulfonamide of Formula I directly as herbicides, it is preferable to use them in mixtures that contain a herbicidally effective amount of the compound together with at least one agriculturally acceptable adjuvant or vehicle. The Suitable adjuvants or vehicles should not be phytotoxic for value crops, particularly in concentrations used in the application of compositions intended for weed control in the presence of the crop, and should not react chemically with the compounds of Formula I or with others Ingredients of the composition. Such mixtures can be designed to be applied directly to weeds or their location, or they can be concentrates or formulations that they are usually diluted with additional vehicles and adjuvants before application. They can be solid, such as, for example, powders, granules, water dispersible granules or powders wettable, or liquids, such as, for example, concentrates emulsifiable, solutions, emulsions or suspensions.

Suitable adjuvants and agricultural vehicles which are useful for preparing the herbicidal mixtures of the invention They are well known to those skilled in the art.

Liquid vehicles that can be used include water, toluene, xylene, petroleum naphtha, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, trichlorethylene, perchlorethylene, ethyl acetate, acetate amyl, butyl acetate, propylene glycol monomethyl ether and ether diethylene glycol monomethyl, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, N-methyl-2-pyrrolidinone and the like Generally, the vehicle chosen for dilution of The concentrates is water.

Suitable solid vehicles include talc, pyrophyllitic clay, silica, attapulgitic clay, kiéselgur, Crete, diatomaceous earth, lime, calcium carbonate, clay bentonite, Fuller's land, cottonseed barks, wheat flour, soy flour, pumice, wood flour, nutmeg, lignin and similar flour.

Frequently, it is desirable to incorporate one or more surface active agents to the compositions herein invention. Said surface active agents are used in advantageous form in both solid and liquid compositions, specially designed to be diluted with a vehicle before of the application. Surface active agents can be anionic, cationic or non-ionic character, and can be used as emulsifying agents, wetting agents, suspension, or for other purposes. Surface active agents Typical include alkyl sulfate salts, such as lauryl sulfate of diethanolammonium; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; addition products of alkylphenol-alkylene oxide, such as C 18 ethoxylate of nonylphenol; alkylene oxide alcohol addition products, such as C 16 ethoxylate of tridecyl alcohol; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulphosuccinate salts, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; amines quaternaries, such as lauryltrimethylammonium chloride; esters polyethylene glycol fatty acids, such as stearate polyethylene glycol; block copolymers of ethylene oxide and propylene's OXID; and salts of mono- and ester esters di-alkyl phosphate.

Other adjuvants commonly used in agricultural compositions include compatibilizing agents, agents defoamers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorizers, extension agents, penetration aides, agents adherent, dispersing agents, thickening agents, depressants of the freezing point, antimicrobial agents and the like. The compositions may also contain other components compatible, for example, other herbicides, insurers herbicides, plant growth regulators, fungicides, insecticides and the like, and can be formulated with fertilizers liquids or vehicles for solid particulate fertilizers, such as ammonium nitrate, urea and the like.

The concentration of active ingredients in The herbicidal compositions of this invention are generally of 0.001 to 98 percent by weight. Concentrations are often used from 0.01 to 90 percent by weight. In compositions designed for be used as concentrates, the active ingredient generally It is present in a concentration between 5 and 98 percent by weight, preferably between 10 and 90 percent. These compositions they are usually diluted with an inert vehicle, such as water, before application. The diluted compositions applied usually to weeds or to the location of the weeds herbs generally contain 0.001 to 5 percent by weight of active ingredient and preferably contain 0.01 to 0.5 per hundred.

The present compositions can be applied to weeds or to your site by using diffusers of aerial or ground level dust, sprayers, and applicators granules, by addition to irrigation water, and through other conventional means known to specialists in the technique.

It has been found that the compounds of Formula I they are pre-emergent herbicides (including before planting) and useful emergency. Applications are generally preferred of post-emergency. The compounds are effective in controlling weeds both broadleaf and herbaceous. Although each of N- (triazoloazinyl) thiophenesulfonamide compounds covered by Formula I is within the scope of the invention, the degree of herbicidal activity, the selectivity for the crop and The weed control spectrum obtained varies depending of the substituents and other features present. The compounds can be used in non-selective application rates superior to control essentially all the vegetation of a area. In some cases, the compounds can also be used in lower selective application rates for the control of undesirable vegetation in arable crops or leaf crops wide In some cases, the selectivity can often be improved through the use of insurers.

The term herbicide is used herein. memory to refer to an active ingredient that controls or adversely modifies plant growth. An amount herbicidally effective or vegetation control is an amount of active ingredient that causes an adverse modifying effect that includes deviations from natural development, death, regulation, dissection, delay, and the like. The terms plants and Vegetation are intended to include germinating seeds, emerging seedlings and established vegetation.

The compounds of the present invention exhibit herbicidal activity when applied directly to the plant or to plant location at any stage of growth or before being planted or emerging. The observed effect depends on the plant species that you want to control, from the stage of plant growth, relative application parameters at dilution and droplet spray size, the size of particle of solid components, of environmental conditions at the time of use, of the specific compound employed, of the specific adjuvants and vehicles used, of the type of soil, and of similar ones, as well as the amount of chemical applied. These and other factors can be adjusted as known. in the technique to promote a selective herbicidal action or not selective Generally, it is preferred to apply the compounds of Formula I possessively emergent to relatively immature plants to achieve maximum weed control.

They are generally used in the operations of Posemergency application rates of 0.001 to 1 kg / ha; for pre-emergency applications, rates of 0.01 to 2 kg / ha. Higher designed rates generally lead to a non-selective control of a wide variety of vegetation not desired. Lower rates typically give selective control. and, through the judicious choice of compounds, chronology and application rates can be used at the location of The crops

The compounds of the present invention (Formula I) are often applied together with one or more other herbicides to gain control of a wider variety of vegetation not desirable. When used in combination with other herbicides, Compounds claimed herein may be formulated with the other or other herbicides, mixed in a tank with the other or other herbicides, or applied sequentially with respect to the other or other herbicides Some of the herbicides that can be used beneficially in combination with the compounds herein invention include triazolopyrimidinsulfonamide compounds substituted, such as diclosulam, chloransulam-methyl and flumetsulam. They can also other herbicides such as acifluorfen, bentazone, chlorimuron, clomazone, lactophen, carfentrazone-methyl, fumiclorac, fluometuron, fomesafén, imazaquín, imazetapir, linrón, metribuzina, fluazifop, haloxyfop, glyphosate, glufosinate, 2,4-D, acetochlor, metolachlor, setoxidim, nicosulfuron, clopiralid, fluroxipir, metsulfuron-methyl, amidosulfuron, tribenuron and others. Generally, it is preferred to use the compounds together with other herbicides that have a similar selectivity to The crops In addition, it is usually preferred to apply the herbicides at the same time, either as a formulation of combination or as a mixture in deposit.

The compounds of the present invention can generally used in combination with a wide variety of known herbicide insurers, such as cloquintocet, mefenpyr, furilazole, dichlormid, benoxacor, flurazole, fluxophenim, daimuron, dimepiperate, thiobencarb and fenclorim, to improve your selectivity. Herbicide insurers that act by modifying the metabolism of herbicides in plants by enhancing the Cytochrome P-450 oxidases activity are usually especially effective. This is often a preferred embodiment of the invention. The compounds can be used additionally to control undesirable vegetation in many crops that have become tolerant to or resistant to herbicides by genetic manipulation or by mutation and selection. For example, crops that have been made can be treated tolerant or resistant to herbicides in general or to herbicides that inhibit the enzyme acetolactate synthase in sensitive plants.

       \ vskip1.000000 \ baselineskip
    

Examples

The following Examples are presented for illustrate the various aspects of this invention.

1. Preparation of 4-Bromo-3-hydroxy-2-thiophenecarboxylate of methyl

To a solution of 31 g (0.2 mol) of 3-hydroxy-2-thiophenecarboxylate of methyl in 400 milliliters (ml) of glacial acetic acid is added 31.3 g (0.2 mol) of Br 2 for 45 minutes (min). After 16 hours (h), another 31.3 g of Br2 were added for 6 h and the reaction stirred another 18 h. Reaction mixture  It was poured into aqueous NaHSO3 and extracted with ether. The phase Organic was separated, washed with water (2 x 300 ml), dried over MgSO4, filtered and concentrated to a viscous oil. This oil (47 g) was dissolved in 200 ml of methanol and, after 48 h at 15 ° C, 36 g (77%) of crystals were collected by filtration light pink mp 79-80 ° C. 1 H NMR (300 MHz, CDCl3): δ 9.8 (an, 1H); 7.4 (s, 1 H); 3.9 (s, 3H). Anal. Calc. For C 6 H 5 BrO 3 S: C, 30.04; H, 2.23; S, 13.52. Found: C, 30.04; H, 1.92; S, 14.01.

2. Preparation of 4-Bromo-3-methoxy-2-thiophenecarboxylate of methyl

To a solution of 36 g (0.15 mol) of 4-Bromo-3-hydroxy-2-thiophenecarboxylate of methyl in 300 ml of dimethylsulfoxide (DMSO) 32 g was added (0.23 mol) of methyl iodide and then 32 g of K 2 CO 3 powder. After 2 h, the reaction mixture is poured into water and extracted with ether. The organic phase was washed with water (4 x 200 ml), dried over MgSO4, filtered and concentrated to give 36 g of a colorless solid. 1 H NMR (300 MHz, CDCl 3): δ 7.4 (s, 1H); 4.0 (s, 3H); 3.9 (s, 3H). Anal. Calc. For C 7 H 7 BrO 3 S: C, 33.48; H, 2.81; S, 12.77. Found: C, 33.18; H, 2.70; S, 12.49.

3. Preparation of 4-Bromo-2-carboxy-3-methoxythiophene

A solution of 37.5 g (0.15 mol) of 4-Bromo-3-methoxy-2-thiophenecarboxylate of methyl and 12 g of KOH (0.18 mol) in a mixture of 250 ml of Methanol and 100 ml of water were refluxed for 2 h. Mix The reaction was cooled and most of the methanol was removed in vacuo. The solution was partitioned with ether and dilute aqueous HCl. The Organic phase was separated, dried over MgSO4, filtered and concentrated and dried under vacuum to give 34 g (94%) of a solid colorless. mp 191-192 ° C. 1 H NMR (300 MHz, CDCl3): δ 7.5 (s, 1H); 4.1 (s, 3H). Anal. Calc. For C 6 H 5 BrO 3 S: C, 30.04; H, 2.23; S, 13.52. Found: C, 29.89; H, 2.06; S, 13.14.

4. Preparation of 4-Bromo-2-carboxy-5-chloro-3-methoxythiophene

A solution of lithium diisopropylamine (LDA) it was prepared at -10 ° C by adding 88.6 ml (0.22 mol) of 2.5M n-butyllithium to a solution of 22.4 g (0.22 mol) of diisopropylamine in 150 ml of Tetrahydrofuran (THF) dry. This was added below. slowly to a colorless solution of 15 g (63 mmol) of 4-Bromo-2-carboxy-3-methoxythiophene  in 200 ml of dry THF at -78 ° C to give a red solution intense. After 1 h, 60 g (0.25 mol) of C 2 Cl 6 and the reaction mixture was allowed to warm slowly up to room temperature The reaction mixture was subjected to cast with ether and dilute aqueous HCl. The organic phase was extracted at then several times with 5% aqueous NaOH. Extracts Aqueous were combined, acidified with 20% aqueous HCl and extracted with recent ether. The organic layer was dried over MgSO 4, filtered and concentrated to give 16.1 g (94%) of a solid cinnamon. mp 191-192 ° C. 1 H NMR (300 MHz, CDCl 3): δ 4.1 (s, 3H). Anal. Calc. For C 6 H 4 BrClO 3 S: C, 26.54; H, 1.48; S, 11.81. Found: C, 27.02; H, 1.55; S, 11.42.

5. Preparation of 4-Bromo-2-carboxy-3-methoxy-5-methylthiophene

A solution of LDA was prepared at -10 ° C by the addition of 101 ml (0.26 mol) of 2.5M n-butyllithium to a solution of 25.6 g (0.26 mol) of diisopropylamine in 150 ml of dry THF. This was then added slowly to a colorless solution of 15 g (63 mmol) of 4-Bromo-2-carboxy-3-methoxythiophene in 200 ml of dry THF at -78 ° C to give a red solution intense. After 1 h, this solution was introduced by means of a cannula in a solution of 60 g (0.42 mol) of methyl iodide in 300 ml of dry THF at -35 ° C. The reaction mixture was subjected to cast with ether and dilute aqueous HCl. The organic layer was dried over MgSO4, filtered and concentrated to a brown solid Sure. This solid was recrystallized from a mixture of hexane and CH 2 Cl 2 to give 11 g of a tan solid. pf 166-167 ° C. 1 H NMR (300 MHz, CDCl 3): δ 3.9 (s, 3H); 2.3 (s, 3H). Anal. Calc. For C 7 H 7 BrO 3 S: C, 33.48; H, 2.81; S, 12.77. Found: C, 33.47; H, 2.77; S, 12.59.

6. Preparation of 3-methoxy-5-trifluoromethyl-2-thiophenecarboxylate of methyl

To a solution of 20 g (88 mmol) of 3-hydroxy-5-trifluoromethyl-2-thiophenecarboxylate of methyl in 200 ml of DMSO 37 g (260 mmol) of iodide were added of methyl and 25 g (181 mmol) of K2CO3 powder. After 2 h stirring, the reaction mixture was poured into water and extracted with ether. The organic phase was separated, washed with water several times, dried over MgSO4, filtered and concentrated to give 20 g of an almost colorless solid. This solid was purified additionally by recrystallization from hexane: ethyl acetate 12: 1 to give 10.5 g of colorless crystals. The mother liquors are concentrated and purified by column chromatography to give another 8 g (87% yield). mp 78-79 ° C. 1 H NMR (300 MHz, CDCl 3): δ 7.2 (s, 1H); 4.0 (s, 3H); 3.9 (s, 3H). Anal. Calc. For C 8 H 7 F 3 O 3 S: C, 40.00; H, 2.94; S, 13.35. Found: C, 39.87; H, 2.94; S, 13.47.

7. Acid preparation 3-methoxy-5-trifluoromethyl-2-thiophenecarboxylic

A solution of 2 g (14 moles) of 3-methoxy-5-trifluoromethyl-2-thiophenecarboxylate of methyl and 2 g (28 moles) of KOH in a mixture of 5 ml of water and 50 ml of methanol was refluxed for 2 h. The mixture of The reaction was partitioned with ether and dilute aqueous HCl. The Organic phase was separated, dried over MgSO4, filtered and concentrated to give 2.8 g (87%) of a colorless solid. pf 131-132 ° C. 1 H NMR (300 MHz, CDC): δ 7.2 (s, 1 H); 4.1 (s, 3H). Anal. Calc. For C 7 H 5 F 3 O 3 S: C, 37.17; H, 2.23; S, 14.18. Found: C, 36.96; H, 2.19; S, 14.08.

8. Acid preparation 4-benzylthio-3-methoxy-5-trifluoromethyl-2-thiophenecarboxylic

To a solution of 3 g (13 mmol) of acid 3-methoxy-5-trifluoromethyl-2-thiophenecarboxylic in 100 ml of dry THF at -20 ° C 5.3 ml (13 mmol) of 2.5M n-butyllithium to form a suspension. To this suspension was added a solution of LDA, freshly prepared by adding 2.0 g (19.7 mmol) of diisopropylamine and 7.9 ml of 2.5M n-butyllithium in 50 ml of THF dry. Over 2 h at 0-5 ° C, the suspension gradually formed a dark solution, before it was added a solution of 9.8 g (40 mmol) of dibenzyl disulfide as a THF solution. The reaction was stirred and allowed to warm to 15 ° C. before it was cast with ether and Na2CO3 diluted aqueous. The aqueous phase was separated, acidified with HCl. 10% aqueous and extracted with fresh ether. The organic phase is separated, concentrated and then purified by HPLC in reverse phase using a 50:50 mixture of acetonitrile and water with 0.5% H 3 PO 4. After most acetonitrile removed in vacuo, the product was recovered from the fraction appropriate by ether extraction. The organic phase separated, dried over MgSO4, filtered and concentrated to give 2 g (43%) of a tan solid. mp 146-147 ° C. 1 H NMR (300 MHz, CDCl 3): δ 9.6 (an, 1H); 7.2 (m, 5H); 4.12 (s, 3H); 4.09 (s, 2H). Anal. Calc. For C 14 H 11 F 3 O 3 S 2: C, 48.27; H, 3.18; S, 18.41. Found: C, 48.00; H, 3.14; S, 18.44.

9. Preparation of 3-benzylthio-4-methoxy-2-trifluoromethylthiophene

A mixture of 3.6 g of 4-benzylthio-3-methoxy-5-trifluoromethyl-2-thiophenecarboxylic acid and 0.85 g of copper powder in 50 ml of quinoline was heated to 150 ° C for 15 min. The mixture was cooled and partitioned with ether and aqueous HCl. The organic phase was separated, dried over MgSO4, filtered, concentrated and purified by column chromatography to give 2.2 g (71%) of an amber oil. 1 H NMR (300 MHz, CDCl 3): δ 7.2 (m, 5H); 6.4 (s, 1 H); 4.1 (s, 2H); 3.8 (s, 3H). Anal. Calcd. For C 13 H 11 F 3 OS 2: C, 51.30; H, 3.64; S, 21.07. Found: C, 51.13; H, 3.54; S,
21.02.

       \ vskip1.000000 \ baselineskip
    

10. Preparation of 3-bromo-4-methoxythiophene

A sample of 15 g of acid 4-Bromo-3-methoxythiophene-2-carboxylic heated to 200-220 ° C at 140 mm vacuum for 40 min. An almost colorless oil (11 g) was collected by distillation. eg 160-165 ° C at 80-85 mm This oil was further purified by chromatography. to give 8.8 g of a colorless oil. 1 H NMR (300 MHz, CDCl3): δ 7.2 (d, 1H, J = 3.5); 6.2 (d, 1H, J = 3.5); 3.9 (s, 3H). Anal. Calc. For C 5 H 5 BrOS: C, 31.11; H, 2.61; S, 16.61. Found: C, 30.98; H, 2.61; S, 16.89.

The following thiophene compounds decarboxylates were prepared similarly:

3-Bromo-4-ethoxythiophene

eg 140-145 ° C at 35 mm. 1 H NMR (300 MHz, CDCl3): δ 7.2 (d, 1H, J = 3.5); 6.2 (d, 1H, J = 3.5); 4.1 (q, 2H, J = 7); 1.5 (t, 3H, J = 7). Anal. Calc. For C 6 H 7 BrOS: C, 34.80; H, 3.41; S, 15.48. Found: C, 34.56; H, 3.36; S, 15.44.

       \ vskip1.000000 \ baselineskip
    

3-Bromo-2-chloro-4-methoxythiophene

eg 160-165 ° C at 10 mm. pf 63-64 ° C. 1 H NMR (300 MHz, CDCl 3): δ 6.1 (s, 1 H); 3.8 (s, 3H). Anal. Calc. For C 5 H 4 BrClOS: C, 26.40; H, 1.77; S, 14.09. Found: C, 26.63; H, 1.76; S, 13.95.

       \ vskip1.000000 \ baselineskip
    

3-Bromo-4-methoxy-2-methylthiophene

eg 150-155 ° C at 10 mm. 1 H NMR (300 MHz, CDCl3): δ 5.9 (s, 1H); 3.7 (s, 3H); 2.3 (s, 3H). Anal. Calc. For C 6 H 7 BrOS: C, 34.80; H, 3.41; S, 15.48. Found: C, 34.66; H, 3.57; S, 15.60.

       \ vskip1.000000 \ baselineskip
    

2-Chloro-4-methoxythiophene

eg 120-125 ° C at 15 mm. 1 H NMR (300 MHz, CDCl 3): δ 6.65 (d, 1H, J = 2); 6.0 (d, 1H, J = 2); 3.8 (s, 3H). Anal. Calc. For C 5 H 5 ClOS: C, 40.41; H 3.20; S, 21.57. Found: C, 40.21; H, 3.20; S, 21.43.

       \ vskip1.000000 \ baselineskip
    

11. Preparation of 5-Chloro-2-chlorosulfonyl-3-methoxythiophene

To a solution of 3.8 g (26 mmol) of 2-chloro-4-methoxythiophene in 100 ml of ether at -30 ° C under nitrogen 11.2 ml was added n-butyllithium This solution is briefly heated to room temperature and then cooled to -60 ° C. This solution was then transferred to a solution of 4 g (85 mmol) of SO2 in 300 ml of ether at -30 ° C to give a thick suspension. This suspension was diluted to facilitate stirring and allowed to warm to temperature ambient. The solids were collected by filtration and were led directly to 75 ml of water before adding 75 ml of isopropyl alcohol. 3.8 g (29 g) were added thereto mmol) of N-chlorosuccinimide. After 30 min, the solution was partitioned with ether and aqueous NaHSO3 diluted. The organic phase was separated, dried over MgSO4, concentrated and purified by HPLC to give 3.1 g of an oil amber. 1 H NMR (300 MHz, CDCl 3): δ 6.8 (s, 1H); 4.1 (s, 3H). Anal. Calc. For C 5 H 4 Cl 2 O 3 S 2: C, 24.30; H, 1.63; S, 25.95. Found: C, 24.10; H, 1.59; S, 25.65.

The following compound of 2-Chlorosulfonylthiophene was prepared Similary:

2-Chlorosulfonyl-3-methoxythiophene

mp 71-72 ° C. 1 H NMR (300 MHz, CDCl 3): δ 7.7 (d, 1H, J = 5.6); 7.0 (d, 1H, J = 5.6); 4.1 (s, 3H). Anal. Calc. For C 5 H 5 ClO 3 S 2: C, 28.24; H, 2.37; S, 30.15. Found: C, 28.41; H, 2.33; S, 30.18.

       \ newpage
    

12. Preparation of 3-chlorosulfonyl-2-methoxythiophene

To a solution of 9 g (47 mmol) of 3-bromo-2-methoxythiophene in 150 ml of dry THF at -78 ° C, 19 ml of slowly added n-butyllithium 2.5 M. After 30 min, the solution was sprayed with excess anhydrous SO2 to precipitate a colorless solid. This mixture was heated until room temperature, diluted with ether and the solid was collected by filtration This solid was dissolved in 150 ml of a mixture Equal isopropyl alcohol and water. They were added to this solution in portions 6.7 g (50 mmol) of N-chlorosuccinimide. After 15 min, the reaction solution was partitioned with ether and dilute aqueous NaHSO3. The organic phase was separated, it was dried over MgSO4, filtered, concentrated and purified by column chromatography to give 5.1 g of an oil amber. 1 H NMR (300 MHz, CDCl 3): δ 6.2 (s, 1H); 3.9 (s, 3H). Anal. Calcd. For C 5 H 5 ClO 3 S 2: C, 28.24; H, 2.37; S, 30.15. Found: C, 28.56; H, 2.57; S, 29.96.

The following compounds of 3-Chlorosulfonylthiophene were prepared Similary:

3-Chlorosulfonyl-4-methoxythiophene

1 H NMR (300 MHz, CDCl 3): δ 8.1 (d, 1H, J = 3.8); 6.4 (d, 1H, J = 3.8); 4.0 (s, 3H). Anal. Calc. For C 5 H 5 ClO 3 S 2: C, 28.24; H, 2.37; S, 30.15. Found: C, 28.24; H, 2.37; S, 29.85.

       \ vskip1.000000 \ baselineskip
    

3-Chlorosulfonyl-4-ethoxythiophene

1 H NMR (300 MHz, CDCl 3): δ 8.1 (d, 1H, J = 3.5); 6.4 (d, 1H, J = 3.5); 4.2 (q, 2H, J = 6.9); 1.2 (t, 3H, J = 6.9). Anal. Calc. For C 6 H 7 ClO 3 S 2: C, 31.79; H, 3.11; S, 28.28. Found: C, 32.07; H, 3.19; S, 27.97.

       \ vskip1.000000 \ baselineskip
    

2-Chloro-3-chlorosulfonyl-4-methoxythiophene

1 H NMR (300 MHz, CDCl 3): δ 6.2 (s, 1 H); 3.9 (s, 3H). Anal. Calc. For C 5 H 5 Cl 2 O 3 S 2: C, 28.24; H, 2.37; S, 30.15. Found: C, 26.40; H, 2.57; S, 29.96.

       \ vskip1.000000 \ baselineskip
    

3-Chlorosulfonyl-4-methoxy-2-methylthiophene

1 H NMR (300 MHz, CDCl 3): δ 6.0 (s, 1 H); 3.8 (s, 3H); 2.6 (s, 3H). Anal. Calc. For C 6 H 7 ClO 3 S 2: C, 28.24; H, 2.37; S, 30.15. Found: C, 28.56; H, 2.57; S, 29.96.

       \ vskip1.000000 \ baselineskip
    

13. Preparation of 3-chlorosulfonyl-4-methoxy-2-trifluoromethylthiophene

A stirred mixture of 5.3 g (17.4 mmol) of 3-benzylthio-4-methoxy-2-trifluoromethylthiophene in 250 ml of CH2Cl2 and 250 ml of dilute aqueous HCl at 0 ° C it was sprayed slowly with 4.7 g of Cl2. The mixture was heated until room temperature and the organic phase was separated, dried over MgSO4, filtered and concentrated to an amber oil. This oil was purified by HPLC to give 3 g of an oil colorless. 1 H NMR (300 MHz, CDCl 3): δ 6.6 (s, 1H); 4.0 (s, 3H). Anal. Calc. For C 6 H 4 ClF 3 O 3 S 2:  C, 25.68; H, 1.44; S, 22.85. Found: C, 25.98; H, 1.5; S, 22.65.

       \ vskip1.000000 \ baselineskip
    

14. Preparation of hydrobromide of 3-amino-8-chloro-5-methylthio [1,2,4] triazolo [4,3-c] pyrimidine

A solution of 40 ml (120 mmol) of bromide 3 molar cyanogen in dichloromethane was combined with 19.0 g (100 mmol) from 5-Chloro-4-hydrazino-2-methylthiopyrimidine and 200 ml of dry isopropyl alcohol at room temperature with agitation. The resulting mixture was stirred for 18 hours and at It was then diluted with 500 ml of diethyl ether. The solids that formed were recovered by filtration and dried to obtain the theoretical amount of the title compound as a yellow solid that melts above 250 ° C. 1 H NMR (DMSO-d6): δ 7.80 (s, 1H); 2.67 (s, 3 H); 13 C: δ 150.96, 147.90, 143.10, 138.38, 113.16, 14.22. Anal. Calc. For C 6 H 7 N 5 BrClS: C, 24.3; H, 2.38; N, 23.6; S, 10.8. Found: C, 26.1; H, 2.69; N, 24.0; S, 12.2.

The following compounds of 3-amino [1,2,4] triazolo [4,3-c] pyrimidine They were prepared similarly:

3-Amino-8-methoxy-5-methylthio [1,2,4] triazolo [4,3-c] pyrimidine hydrobromide - a tan-colored solid that melts at 180-182 ° C; Anal. Calcd. For C 7 H 10 N 5 BrOS: C, 28.8; H, 3.45; N, 24.0; S, 11.0. Found: C, 29.0; H, 3.44; N, 23.9; S, 11.1.

3-Amino-8-methyl-5-methylthio [1,2,4] triazolo [4,3-c] pyrimidine hydrobromide - a yellow solid that melts at 234-236 ° C; Anal. Calc. For C 7 H 10 N 5 BrS: C, 30.6; H, 3.30; N, 25.5; S, 11.7. Found: C, 30.7; H, 3.52; N, 25.3; S, 11.5.

15. Preparation of 2-amino-8-chloro-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidine

A mixture of 15.0 g (51 mmol) of hydrobromide from 3-amino-8-chloro-5-methylthio [1,2,4] triazolo [4,3-c] pyrimidine,  8.2 ml (76 mmol) of ethyl acrylate and 150 ml of methanol are He prepared and cooled in an ice bath. A solution of 17 ml (76 mmol) of 4.5 molar sodium methoxide was added to this slowly with cooling and stirring When the addition was complete, the mixture it was allowed to warm to room temperature and stirred for 18 hours. It was neutralized with 2.0 ml acetic acid. The solids that they formed were recovered by filtration, washed with ether diethyl and dried to obtain 7.7 g (75 percent of the theory) of the title compound as a tan powder which melts above 250 ° C. 1 H NMR (DMSO-d6): δ 8.0 (s, 1H); 6.6 (s an, 2H); 4.1 (s, 3H); 13 C: δ 166.40, 151.65, 147.73, 140.95, 108.57, 56.12. Anal. Calc. For C 6 H 6 N 5 ClO: C, 36.1; H, 3.03; N, 35.1. Found: C, 36.1; H, 3.19; N, 34.8.

The following compounds of 2-amino [1,2,4] triazolo [1,5-c] pyrimidine They were prepared similarly:

2-Amino-5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidine - a cinnamon-colored powder that melts at 201-203 ° C; Anal. Calcd. For C 7 H 9 N 5 O 2: C, 43.1; H, 4.65; N, 35.9. Found: C, 43.2; H, 4.67; N, 35.6.

2-Amino-8-methyl-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidine - a tan-colored solid that melts above 250 ° C; Anal. Calcd. For C 7 H 9 N 5 O: C, 46.9; H, 5.06; N, 39.1. Found: C, 46.7; H, 4.84; N, 39.1.

       \ vskip1.000000 \ baselineskip
    

16. Preparation of 2-amino-5,8-dimethoxy [1,2,4] triazolo [1,5-a] pyridine

A mixture of 58.4 g (0.21 mol) of [(3,6-dimethoxypyridin-2-yl) amino] carbonothioylcarbamate ethyl, 70 g (1 mol) of hydroxylamine hydrochloride and 105 ml (0.6 mol) of diisopropylethylamine in 1 liter of ethanol was heated until reflux for 12 h. After cooling, the solution resulting evaporated to dryness under vacuum. They were added to water residue (250 ml) and diethyl ether (100 ml) and the mixture was stirred for 15 min. The product was collected by filtration and was dried under vacuum at room temperature to give 25.2 g of 2-amino-5,8-dimethoxy [1,2,4] triazolo [1,5-a] pyridine. mp 223-234 ° C. 1 H NMR (DMSO-d 6): δ 6.9 (d, 1H, J = 8.7); 6.2 (d, 1H, J = 8.4); 5.9 (s, 2H); 4.0 (s, 3H); 3.8 (s, 3H).

       \ vskip1.000000 \ baselineskip
    

17. Preparation of 2-amino-5,7-dimethoxy [1,2,4] triazolo [1,5-a] pyrimidine

2-Amino-4,6-dimethoxypyrimidine (5.0 g, 36 mmol) was dissolved in dry tetrahydrofuran (THF, 35 ml), ethoxycarbonyl isothiocyanate (6.4 ml, 54 mmol) was added and the solution was allowed to stir at room temperature. After 24 hours, the solvent was removed in vacuo and the residue was mixed with ether to form a crystalline solid. The solids were removed by vacuum filtration and dried to provide [(4,6-dimethoxypyrimidin-2-yl) amino] carbonothioylcarbamate  ethyl as a tan solid (8.9 g, 87%). pf 196-197 ° C. 1 H NMR (CDCl 3): δ 13.2 (s at, 1 H); 8.8 (s at, 1 H); 5.80 (s, 1 H); 4.32-4.25 (q, 2H, J = 7.2); 3.93 (s, 3 H); 1.30 (t, 3H, J = 7.2).

Ethyl (4,6-Dimethoxypyrimidin-2-yl) aminocarbonothioylcarbamate (0.50 g, 1.7 mmol) was mixed with ethanol (5 ml). To this mixture were added hydroxylamine hydrochloride (0.12 g, 1.7 mmol) and diisopropylethylamine (0.30 ml, 1.7 mmol). The resulting mixture was allowed to stir at room temperature. After 2.5 hours, additional diisopropylethylamine (0.30 ml, 1.7 mmol) was added to the mixture. After 48 hours the ethanol was removed in vacuo and the residue was partitioned between H2O and Et2O to give a powder. The powder was filtered and dried to provide the product as a tan powder (0.27 g, 82%). mp 215-220 ° C. Anal .: Calcd. For C 7 H 9 N 5 O 2: C, 43.08; H, 4.65; N, 35.88; O, 16.39; Found: C, 39.88; H, 4.22; N, 32.00; Or, 16.35. 1 H NMR (DMSO-d 6): δ 6.04 (s, 1H); 5.97 (an, 2H); 4.04
(s, 3H).

       \ vskip1.000000 \ baselineskip
    

18. Preparation of 3-methoxy-N- (5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-yl) thiophene-2-sulfonamide (Compound 1)

At a suspension of 0.8 g (4.5 mmol) of 2-amino-5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidine in 1.3 ml of acetonitrile, 1.3 g (6.1 mmol) of chloride were added. 3-methoxythiophene-2-sulfonyl, 0.6 ml of dry pyridine and 0.003 ml of dry DMSO. After 96 h, the reaction mixture was partitioned with CH2Cl2 and Water. The organic phase was separated, washed with dilute aqueous HCl, dried over MgSO4, filtered and concentrated. The residue is collected in a small amount of CH2Cl2 before it add ether slowly with stirring to precipitate a solid Fine cinnamon color. The solid was collected by filtration and was dried under vacuum to give 0.85 g (50%) of the desired product. pf 227-228 ° C. 1 H NMR (300 MHz, DMSO-d6): δ 12.1 (s, 1H); 7.8 (d, 1H, J = 5.6); 7.6 (s, 1 H); 7.0 (d, 1H, J = 5.6); 4.1 (s, 3H); 3.9 (s, 3H); 3.8 (s, 3H). Calcd. For Cl 2 H 13 N 5 O 5 S 2: C, 38.81; H, 3.53; N, 18.86; S, 17.27. Found: C, 38.32; H, 3.49; N, 18.91; S, 17.34.

The compounds of N - ([1,2,4] triazolo [1,5-c] pyrimidin-2-yl) thiophenesulfonamide, N - ([1,2,4] triazolo [1,5-a] pyrimidin-2-yl) thiophenesulfonamide  Y N - ([1,2,4] triazolo [1,5-a] pyridin-2-yl) thiophenesulfonamide Tables 1 and 2 were prepared similarly.

19. Preparation of Herbicidal Compositions Wettable Powder

Barden clay (55.5 g), HiSil 233 silica (5.0 g), Polyfon H (sodium lignosulfonate; 7.0 g), Stepanol ME-Dry (sodium lauryl sulfate; 7.9 g) and Compound 1 (20.4 g) were added to a Waring combination vessel of 0.95 liters (1 quarter) and mixed thoroughly at high speed. The combined mixture was passed (once) through a mill of laboratory Trost with opposite jets set between 517 and 551 kPa (75-80 psi). This produced a dust wettable with excellent wetting capacity and power suspension. By diluting this wettable powder with water it is possible obtain suspensions of adequate concentrations to control weeds.

Aqueous Suspension Concentrate

To prepare a concentrate for suspensions aqueous, deionized water (106 g), Kelzan S (xanthan gum; 0.3 g), Avicel CL-611 (carboxymethyl cellulose; 0.4 g) and Proxel GXL (1,2-benzothiazolin-3-one; 0.2 g) were added to a combination device and mixed for 30 min. Next, Compound 6 (44 g), Darvan # 1 (naphthalenesulfonate; 2 g), Foamaster UDB (silicone fluid; 0.2 g), Pluronic P-105 (oxide block copolymer of ethylene / propylene oxide; 20 g), phosphoric acid (0.02 g) and Propylene Glycol (16 g) were added to the same device combination and mixed for 5 min. Once combined, the content was ground in an Eiger mill loaded with beads lead-free glass 1-1.25 mm (40 ml) at 5000 rpm for 30 min. The external cooling of the chamber of Crushing of the Eiger mill was maintained at 15 ° C.

Concentrate for Oil Based Suspensions

To a Waring combination vessel of 0.95 liter glass (1 quart) vegetable oil was added from Exxon (145.4 g), Amsul DMAP 60 (acid dimethylaminopropane salt dodecylbenzenesulfonic; 4.0 g) and Attagel 50 (attapulgitic clay; 4.0 g). The mixture was thoroughly combined at high speed to ensure homogeneity The Amsul DMAP was difficult to disperse, but finally it formed small homogeneous blood cells. Agrimul 70-A (ethoxylated bismethylenectylphenol; 4.0 g) and Emulsogen M (oleyl alcohol-ethylene oxide; 16.0 g) were added  and combined thoroughly until the mixture had uniform texture. Cloquintocet-mexyl (5.4 g) was combined to then in the mixture, followed by Compound 7 (21.3 g). The Reserve dispersion for final crushing was milled in the mill of Eiger using the conditions described above for the concentrate for aqueous suspensions.

       \ vskip1.000000 \ baselineskip
    

20. Evaluation of Herbicidal Activity of Posemergence

Seeds of test plant species desired planted in planted mix Grace-Sierra MetroMixe 306, which typically has a pH of 6.0 to 6.8 and an organic matter content of approximately 30 percent, in plastic pots with a surface area of 64 square centimeters. When it was necessary for ensure good germination and obtaining plants healthy, a fungicide treatment and / or other chemical or physical treatment The plants were grown during 7-21 days in a greenhouse with a photoperiod of approximately 15 h that was maintained at approximately 23-29ºC during the day and 22-28ºC overnight. Nutrients and water were added regularly and provided complementary light with 1000 watt lamps high metal halide, as necessary. The plants were used to evaluate the moment at which the first one is reached and Second true leaf stages.

A heavy amount of each test compound, determined by the highest rate to be tested, it was put in a 20 ml glass vial and dissolved in 4 ml of a 97: 3 v / v mixture (volume / volume) of acetone and dimethylsulfoxide to obtain concentrated reserve solutions. If the test compound is not easily dissolved, the mixture was heated and / or subjected to ultrasound The concentrated stock solutions were diluted with an aqueous mixture containing acetone, water, alcohol isopropyl, dimethylsulfoxide, vegetable oil concentrate Atplus 411F and Triton X-155 surfactant (methylenebisdiamilphenoxypolyethoxyethanol) in a relationship 48.5: 9: 10: 1.5: 1.0: 0.02 v / v to obtain spray solutions of known concentration. The solutions that contained the highest concentration to be tested were prepared by diluting 2 ml aliquots of the stock solution with 13 ml of the mixture and lower concentrations were prepared by dilution of appropriate minor portions of the stock solution. Aliquots of approximately 1.5 ml of each solution of known concentration were sprayed evenly over each of pots with test plants using a DeVilbiss atomizer moved by compressed air at a pressure of 140 to 280 kilopascals (2 to 4 psi) to obtain a complete coating of each plant. Similarly control plants were sprayed with the mixture watery In this test, an application rate of 1 ppm gives as result the application of approximately 1 g / ha.

The treated plants and control plants were placed in a greenhouse as described above, and were watered by sub-irrigation to avoid washing by washing of test compounds. After 2 weeks the condition of the test plants was visually compared with that of untreated plants and was scored on a scale of 0 to 100 percent, where 0 corresponds to the absence of injuries and 100 corresponds to a total elimination. Some of the compounds evaluated, application rates used, plant species evaluated and the results obtained are shown in Table 3.

fifteen

16

21. Evaluation of Herbicidal Activity of Pre-emergency

Seeds of the desired plant species are planted in a soil matrix prepared by mixing a soil clay that was composed of approximately 43 percent of slime, 19 percent clay and 38 percent sand and had a pH of approximately 8.1 and an organic matter content of approximately 1.5 percent and sand in a ratio of 70 to 30. The soil matrix was introduced in plastic pots with an area surface area of 161 square centimeters. When it was necessary for ensure good germination and obtaining plants healthy, a fungicide treatment and / or other chemical or physical treatment

A 20 ml glass vial was placed heavy amount, determined by the highest rate to be tested, of each test compound and dissolved in 8 ml of a 97: 3 mixture v / v (volume / volume) of acetone and dimethylsulfoxide to obtain concentrated reserve solutions. If the test compound does not dissolved easily, the mixture was heated and / or subjected to ultrasound The stock solutions obtained were diluted with a 99.9: 0.1 mixture of water and Tween® 155 surfactant (ester of ethoxylated sorbitan fatty acid) to obtain solutions of application of known concentration. The solutions they contained the highest concentration to be tested were prepared at dilute 4 ml aliquots of the stock solution with 8.5 ml of the mixture and the lower concentrations were prepared by diluting appropriate minor portions of the solution backup. A 2.5 ml aliquot of each solution of known concentration was sprayed evenly on the ground of each pot planted using a 5.0 ml glass syringe Cornwall equipped with a hollow conical nozzle TeeJet TN-3 to obtain total soil coverage of each pot. Of the same  so control pots were sprayed with the aqueous mixture. Rate Highest application of 4.48 kg / ha is reached when used 50 mg of test compound.

The treated pots and the control pots are put in a greenhouse with a photoperiod of about 15 h which was maintained at approximately 23-29 ° C for the day and 22-28 ° C overnight. They were added nutrients and water regularly and complementary light was provided with 1000 watt high metal halide lamps, according to It was necessary. Water was added by superior irrigation. After 3 weeks the condition of the evaluated plants that germinated and grew compared to untreated plants that germinated and grew, and scored on a scale from 0 to 100 percent, where 0 corresponds to absence of injuries and 100 corresponds to a complete elimination or not germination. Some of the compounds evaluated, rates of application used, plant species evaluated and the results obtained are shown in Table 4.

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

17

18

Claims (11)

1. A compound of N - (triazoloazinyl) thiophenesulfonamide of the formula (I):

         \ vskip1.000000 \ baselineskip
      

19

         \ vskip1.000000 \ baselineskip
      

at that X represents CH or N; Y represents CZ or N, with the proviso that X e And they are not both N; W represents H or OR, with the proviso that when Y is CZ, then W is H; Z represents R, OR or halo; D and E represent S or CB, with the condition of that one of D or E is S; A represents OR 'or CO 2 R' ', and B represents H, halo, CF 3, R or R 7 or CO 2 R ''; T represents H, SO2R '', C (O) R '', C (O) OR '', C (O) NR '' 2 or CH 2 CH 2 C (O) OR ''; R represents CH 3 or CH 2 CH 3; R 'represents alkyl C 1 -C 4, alkenyl C 3 -C 4 or alkynyl C_ {3} -C_ {4}, each optionally possessing Up to two substituents chlorine, bromine or O (C 1 -C 4) alkyl or up to the maximum possible number of fluoro substituents; R '' represents H or alkyl C 1 -C 4; and, when T represents H, its salts agriculturally acceptable.

         \ vskip1.000000 \ baselineskip
      

2. A compound according to claim 1, in which T represents H or one of its salts agriculturally acceptable. 3. A compound according to claim 1 or claim 2, wherein X represents N, Y represents CZ and W represents H. 4. A compound according to claim 1 or claim 2, wherein X represents CH and Y represents N. 5. A compound according to claim 1 or claim 2, wherein X represents CH, Y represents CZ and W represents H. 6. A compound according to any one of the preceding claims, wherein D represents S and E represents CB. 7. A compound according to any one of the preceding claims, wherein B represents CO_ {2} R ''. 8. A composition comprising an amount herbicide of a compound of N- (triazolopyrimidin) thiophenesulfonamide according to a any of claims 1-7 mixed with an agriculturally acceptable adjuvant or vehicle. 9. A method to control vegetation does not desirable that includes applying to the vegetation or its location a herbicidally effective amount of a compound of N- (triazolopyrimidin) thiophenesulfonamide according to a any of claims 1-7.

         \ newpage
      

10. A procedure for the preparation of a N- (triazolopyrimidin) thiophenesulfonamide compound of according to claim 1, which comprises contacting a compound of the formula (II): twenty

         \ vskip1.000000 \ baselineskip
      

with a chloride compound of thiophenesulfonyl of formula III: twenty-one in which A, D, E, R, W, X and Y are as defined for the compounds of Formula I in a solvent polar aprotic under anhydrous conditions and add pyridine as a base and a catalytic amount of dimethylsulfoxide. 11. Use of a chloride compound of thiophenesulfonyl of Formula III for the manufacture of a compound of Formula I according to claim 10: 22 at that D and E represent S or CB, with the condition of that one of D or E is S; A and B independently represent H, halo, CF_ {3}, R, OR 'or CO2_R' ', provided that at least one of A or B represents OR 'or CO 2 R' '; R represents CH 3 or CH 2 CH 3; R 'represents alkyl C 1 -C 4, alkenyl C 3 -C 4 or alkynyl C_ {3} -C_ {4}, each optionally possessing Up to two substituents chlorine, bromine or O (C 1 -C 4) alkyl or up to the maximum possible number of fluoro substituents; Y R '' represents H or alkyl C_ {1} -C_ {4}, with the conditions that when D represent S and A represent H, then B does not represent CO 2 R ''; when D represents S and B represents H, then A does not represent CO 2 R ''; when E represents S and B represents H, then A does not represent CO 2 R ''; or when E represents S and B represent H, then A does not represent OCH_ {3}.